EP3302785B1 - Method for preparing a sorbent - Google Patents
Method for preparing a sorbent Download PDFInfo
- Publication number
- EP3302785B1 EP3302785B1 EP16721890.8A EP16721890A EP3302785B1 EP 3302785 B1 EP3302785 B1 EP 3302785B1 EP 16721890 A EP16721890 A EP 16721890A EP 3302785 B1 EP3302785 B1 EP 3302785B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- copper
- sorbent
- alumina
- sulphide
- particulate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
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- 239000002594 sorbent Substances 0.000 title claims description 57
- 238000000034 method Methods 0.000 title claims description 51
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 41
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 36
- 239000012530 fluid Substances 0.000 claims description 22
- 239000010949 copper Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000008187 granular material Substances 0.000 claims description 11
- 229910001385 heavy metal Inorganic materials 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 8
- 239000005749 Copper compound Substances 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 150000001880 copper compounds Chemical class 0.000 claims description 7
- 238000007493 shaping process Methods 0.000 claims description 7
- 239000005864 Sulphur Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 25
- 229930195733 hydrocarbon Natural products 0.000 description 15
- 150000002430 hydrocarbons Chemical class 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000004215 Carbon black (E152) Substances 0.000 description 12
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 12
- 229910052753 mercury Inorganic materials 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 239000002250 absorbent Substances 0.000 description 7
- 230000002745 absorbent Effects 0.000 description 7
- 230000032683 aging Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 229910052955 covellite Inorganic materials 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 229910052976 metal sulfide Inorganic materials 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229940116318 copper carbonate Drugs 0.000 description 3
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910021653 sulphate ion Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- QLNFINLXAKOTJB-UHFFFAOYSA-N [As].[Se] Chemical compound [As].[Se] QLNFINLXAKOTJB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910001680 bayerite Inorganic materials 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 description 1
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical class [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940013317 fish oils Drugs 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- -1 monoxide hydroxides Chemical class 0.000 description 1
- 229910001682 nordstrandite Inorganic materials 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000012492 regenerant Substances 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000002641 tar oil Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0285—Sulfides of compounds other than those provided for in B01J20/045
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
- B01J20/0237—Compounds of Cu
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
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- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
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- C01F1/00—Methods of preparing compounds of the metals beryllium, magnesium, aluminium, calcium, strontium, barium, radium, thorium, or the rare earths, in general
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/10—Refining fats or fatty oils by adsorption
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
- C10L2290/542—Adsorption of impurities during preparation or upgrading of a fuel
Definitions
- This invention relates to a method for preparing a sorbent based on a mixture consisting of a particulate copper sulphide and a particulate calcined, rehydratable alumina.
- Copper sulphide containing sorbents are useful in removing heavy metals from fluid streams.
- Heavy metals such as mercury are found in small quantities in fluid streams such as hydrocarbon or other gas and liquid streams.
- Arsenic and antimony may also be found in small quantities in hydrocarbon streams.
- Mercury in addition to its toxicity, can cause failure of aluminium heat exchangers and other processing equipment. Therefore there is a need to efficiently remove these metals from fluid streams, preferably as early as possible in the process flowsheet.
- Copper sulphide is conventionally formed in the sorbents either in situ by reaction of a sorbent precursor containing a sulphidable copper compound with hydrogen sulphide (H 2 S) present in the fluid stream, or by pre-sulphiding the sorbent precursor again with hydrogen sulphide. This reaction is depicted for copper oxide as follows: CuO + H 2 S ⁇ CuS + H 2 O
- WO2009/101429 discloses a method for making an absorbent comprising the steps of: (i) forming a composition comprising a particulate copper compound capable of forming copper sulphide, a particulate support material, and one or more binders, (ii) shaping the composition to form an absorbent precursor, (iii) drying the absorbent precursor material, and (iv) sulphiding the precursor to form the absorbent.
- the sulphiding agent used to sulphide the absorbent precursor may be one or more sulphur compounds such as hydrogen sulphide, carbonyl sulphide, mercaptans and polysulphides, or mixtures of these. Hydrogen sulphide is preferred.
- US2013202503 discloses a process for removing mercury from a fluid stream comprising contacting the fluid stream with a sorbent comprising cupric sulfide.
- the cupric sulfide is formed from direct sulfidation of copper carbonate, without thermal decomposition of the copper carbonate to an oxide, at a temperature less than about 150° C.
- WO2011081836 discloses a process for the removal of mercury from a mixture of saturated and unsaturated hydrocarbons such as from cracked gas.
- the gas first is contained in a regenerable adsorbent bed that removes water and mercury and then the regenerant stream for the adsorbent bed is passed through a non-regenerable bed comprising copper sulfide to trap the mercury.
- US2014155260 discloses a process for removing mercury from a gas or liquid phase, wherein the gas or liquid phase containing mercury is placed in contact with a composition comprising a precipitated metal sulfide.
- the precipitated metal sulfide may be made by the process of combining a metal source, sulfide source, and modifier to form the precipitated metal sulfide.
- US2007122327 discloses sorbents for removal of mercury and other pollutants from gas streams and methods for their manufacture and use.
- the methods include mixing sorbent substrate particles with a sulfide salt and a metal salt to form a metal sulfide on the outer surface of the sorbent particles.
- the invention provides a method for preparing a sorbent comprising the steps of:
- the invention further provides a method for removing heavy metals such as mercury, arsenic selenium, cadmium and antimony, from heavy metal-containing fluid stream by preparing a sorbent according with the above method and contacting the fluid stream with the sorbent.
- heavy metals such as mercury, arsenic selenium, cadmium and antimony
- absorbent we include absorbent and adsorbent.
- calcined, rehydratable alumina we mean a calcined amorphous or poorly crystalline transition alumina comprising one or more of rho-, chi- and pseudo gamma-aluminas. Such aluminas are capable of rehydration and can retain substantial amounts of water in a reactive form.
- Calcined, rehydratable aluminas are commercially available, for example as "CP alumina powders” available from BASF AG. They may be prepared, for example, by milling gibbsite (Al(OH) 3 ), to a 1-20 micron particle size followed by flash calcination for a short contact time as described in U.S. patent No. 2,915,365 .
- amorphous aluminum hydroxide and other naturally found mineral crystalline hydroxides such as Bayerite and Nordstrandite or monoxide hydroxides, such as Boehmite (AIOOH) and Diaspore may be also used as a source of the calcined, rehydratable alumina.
- AIOOH Boehmite
- Diaspore may be also used as a source of the calcined, rehydratable alumina.
- the particulate copper sulphide used to prepare the sorbent may be sourced commercially or may be prepared by a number of methods. Suitable methods include roasting of copper or a copper compound with elemental sulphur, solvothermal processes, hydrothermal processes (e.g. microwave irradiation), electrodeposition techniques, precipitation of copper sulphide from solution, sulphiding of copper compounds using hydrogen sulphide, electron irradiation or by a mechanochemical process in which powdered copper metal is mixed with elemental sulphur under conditions that cause the elemental copper and elemental sulphur to react to form one or more copper sulphides. Such methods are described in the Materials Research Bulletin, vol 30, no 12, p1495-1504, 1995 .
- Copper sulphides that may be used include Copper (II) sulphide, CuS, (covellite) and/or substoichiometric copper sulphides, e.g. of formula Cu 2-x S where x is 0-1, such as Cu 9 S 5 (digenite).
- copper sulphides may be used. Copper sulphides high in CuS are preferred, and the overall S:Cu atomic ratio of the particulate copper sulphide is preferably ⁇ 0.8, more preferably ⁇ 0.9, most preferably ⁇ 0.95. Desirably, essentially all of the sulphided copper in the sorbent is in the form of copper (II) sulphide, CuS.
- the particulate copper sulphide may be in the form of a powder, preferably a powder with an average particle size, i.e. Dso, in the range 5-100 ⁇ m.
- the dried sorbent may comprise 5-75% by weight, preferably 10-75% by weight, more preferably 15-55% by weight, especially 15-50% by weight, of copper sulphide (expressed as CuS).
- the particulate calcined, rehydratable alumina is preferably an amorphous or poorly crystalline transition alumina comprising one or more of rho-alumina, chi-alumina and pseudo-gamma alumina.
- the particulate calcined, rehydratable alumina consists of one or more of rho-alumina, chi-alumina and pseudo-gamma alumina, especially rho-alumina.
- the particulate calcined, rehydratable alumina is desirably in the form of a powder, more preferably a powder with a D 50 particle size in the range 1-100 ⁇ m, preferably 1-20 ⁇ m, especially 1-10 ⁇ m.
- the BET Surface area of the calcined, rehydratable alumina as determined by nitrogen adsorption may be in the range 200-400m 2 /g, preferably 250-300m 2 /g.
- the dried sorbent may comprise 25-95% by weight, preferably 25-90% by weight, of the particulate calcined, rehydratable alumina.
- the first step in the method for preparing the sorbent comprises forming a mixture consisting of the particulate copper sulphide and the particulate calcined, rehydratable alumina.
- the sorbent may be considered to be "binderless”.
- the sorbent is made from a mixture that consists of copper sulphide and the particulate calcined, rehydratable alumina.
- sorbent pellets may be formed by moulding a powder composition, generally containing a material such as graphite or magnesium stearate as a moulding aid, in suitably sized moulds, e.g. as in conventional tableting operation.
- sorbent extrudates may be formed by forcing a suitable composition and often a little water and/or a moulding aid as indicated above, through a die followed by cutting the material emerging from the die into short lengths.
- extrudates may be made using a pellet mill of the type used for pelleting animal feedstuffs, wherein the mixture to be pelleted is charged to a rotating perforate cylinder through the perforations of which the mixture is forced by a bar or roller within the cylinder: the resulting extruded mixture is cut from the surface of the rotating cylinder by a doctor knife positioned to give extruded pellets of the desired length.
- sorbent granules in the form of agglomerates, may be formed by mixing a powder composition with a little liquid, such as water, insufficient to form a slurry, and then causing the composition to agglomerate into roughly spherical granules in a granulator.
- the amount of liquid added will vary depending upon the porosity and wettability of the components, but may be 0.1 to 0.5 ml/g of support mixture.
- Aqueous or non-aqueous liquids may be used, but water is preferred.
- Minimizing the amount of liquid used advantageously reduces the drying time of the sorbent and may reduce the formation of undesirable copper sulphates.
- granulating the mixture under a non-oxidising atmosphere, such as oxygen-free nitrogen reduces the potential formation of sulphates. Suitable granulator equipment is available commercially.
- the liquid may be conveniently added by spraying.
- the pellets, extrudates or granules preferably have a length and width in the range 1 to 25 mm, with an aspect ratio (longest dimension divided by shortest dimension) ⁇ 4.
- a preferred shaping method involves granulating the mixture of copper sulphide and calcined, rehydratable alumina in a granulator.
- Granules with a diameter in the range 1-15 mm are preferred.
- the amount of water used in granulating the mixtures has been found to have an influence on the strength of the resulting granules.
- the amount of water used in the granulation may be in the range 0.25ml/g of powder to 0.6ml/g of the mixture of copper sulphide and calcined, rehydratable alumina. This is higher than the prior art granulated products that typically require ⁇ 0.2ml/g of mixture and arises from the unusual properties of the calcined, rehydratable alumina.
- the shaped absorbent may be aged to enhance its strength before drying.
- Ageing of the calcined, rehydratable alumina-containing sorbents is suitably performed at 20-90°C, preferably 40-90°C.
- An advantage of using just the calcined, rehydratable alumina in the sorbent is that the ageing step may be considerably reduced or eliminated compared to prior art materials.
- ageing may be performed on calcined, rehydratable alumina containing granules for 0.5 - 8 hours, preferably 0.5-6 hours, more preferably 0.5-2 hours before drying.
- Ageing under a non-oxidising atmosphere such as dry nitrogen reduces the potential for sulphate formation.
- the shaped sorbent is dried. Conventional drying equipment may be used. Drying temperatures up to 120°C may be used. Drying times may be in the range 0.25-16 hours. Drying under a non-oxidising atmosphere such as dry nitrogen reduces the potential for sulphate formation.
- the sorbent may be used to treat both liquid and gaseous fluid streams containing heavy metals, in particular fluids containing mercury and/or arsenic.
- the fluid stream is a hydrocarbon stream.
- the hydrocarbon stream may be a refinery hydrocarbon stream such as naphtha (e.g. containing hydrocarbons having 5 or more carbon atoms and a final atmospheric pressure boiling point of up to 204°C), middle distillate or atmospheric gas oil (e.g. having an atmospheric pressure boiling point range of 177°C to 343°C), vacuum gas oil (e.g.
- Refinery hydrocarbon steams also include carrier streams such as "cycle oil” as used in FCC processes and hydrocarbons used in solvent extraction.
- the hydrocarbon stream may also be a crude oil stream, particularly when the crude oil is relatively light, or a synthetic crude stream as produced from tar oil or coal extraction for example.
- Gaseous hydrocarbons may be treated using the process of the invention, e.g. natural gas or refined paraffins or olefins, for example.
- Off-shore crude oil and off-shore natural gas streams in particular may be treated with the sorbent.
- Contaminated fuels such as petrol or diesel may also be treated.
- the hydrocarbon may be a condensate such as natural gas liquid (NGL) or liquefied petroleum gas (LPG), or gases such as a coal bed methane, landfill gas or biogas.
- Gaseous hydrocarbons, such as natural gas and associated gas are preferred.
- Non-hydrocarbon fluid streams which may be treated include carbon dioxide, which may be used in enhanced oil recovery processes or in carbon capture and storage, solvents for decaffeination of coffee, flavour and fragrance extraction, solvent extraction of coal etc.
- Fluids such as alcohols (including glycols) and ethers used in wash processes or drying processes (e.g. triethylene glycol, monoethylene glycol, RectisolTM, PurisolTM and methanol), may be treated by the inventive process.
- Mercury may also be removed from amine streams used in acid gas removal units.
- Natural oils and fats such as vegetable and fish oils may be treated, optionally after further processing such as hydrogenation or transesterification e.g. to form biodiesel.
- Other fluid streams that may be treated include the regeneration gases from dehydration units, such as molecular sieve off-gases, or gases from the regeneration of glycol driers.
- the sorbent is of utility where the fluid stream contains water, preferably in low levels in the range 0.02 to 1% vol. Higher levels up to 5% vol may be tolerated for short periods.
- the sorbents may be regenerated simply after prolonged exposure to water simply by purging with a dry gas, preferably a dry inert gas such as nitrogen.
- the sorption of heavy metal is conducted at a temperature below 150°C, preferably at or below 120°C in that at such temperatures the overall capacity for heavy metal absorption is increased. Temperatures as low as 4°C may be used. A preferred temperature range is 10 to 60°C.
- the gas hourly space velocity through the sorbent may be in the range normally employed.
- the sorbent may be used to treat both liquid and gaseous fluid streams containing one or more reductants such as hydrogen and/or carbon monoxide, notably hydrogen.
- the fluid stream is a liquid hydrocarbon stream containing dissolved hydrogen and/or carbon monoxide.
- the fluid stream is a gaseous stream containing hydrogen and/or carbon monoxide, i.e. a reducing gas stream.
- Gas streams that may benefit from this process include synthesis gas streams from conventional steam reforming processes and/or partial oxidation processes, and synthesis gas streams from a coal gasifier, e.g. as part of a IGCC process, after gas washing and heat recovery (cooling) steps, and before the sour shift stage.
- streams that may benefit from the present invention include refinery vent streams, refinery cracker streams, blast furnace gases, reducing gases, particularly hydrogen-rich gas streams, ethylene-rich streams and liquid or gaseous hydrocarbon streams, e.g. naphtha, fed or recovered from hydrotreating processes, such as hydrodesulphurisation or hydrodenitrification.
- the sorbent may be placed in a sorption vessel and the fluid stream containing heavy metal is passed through it.
- the sorbent is placed in the vessel as one or more fixed beds according to known methods. More than one bed may be employed and the beds may be the same or different in composition.
- a mixture of a copper sulphide powder and a calcined, rehydratable alumina powder was prepared as follows: Component Source % wt Copper sulphide (99%), Eurolub 33 Calcined, rehydratable alumina CP-5, BASF 67
- the properties of the calcined, rehydratable alumina powder were as follows: Chemical composition (wt %) Residual Moisture (dried a 250°C for 30 minutes) 2 Total loss on ignition (250-1100°C) 7 SiO 2 ⁇ 0.02 Fe 2 O 3 ⁇ 0.01 Na 2 O ⁇ 0.4 Physical Properties BET Surface area 270 m 2 /g Packed bulk density 38 Ib/ft 3 Particle size distribution (average size) 5 ⁇ m Particle size distribution (90 wt% ⁇ ) 12 ⁇ m XRD Phase Amorphous
- the powders were pre-mixed to ensure a homogenous mixture.
- Granules were then formed by nodulizing the mixture in a rotating pan while water (about 0.33ml/g mixture) was sprayed onto the mixture as a fine mist.
- the water was found to be about 25 wt% of the mass of the shaped agglomerates before drying. This is significantly higher than the water content of the prior granulated sorbents which typically only comprise about 15 wt% water.
- the material was aged at 45°C. Following ageing, the material was dried in a fluid bed dryer at 105°C, to produce the sorbent.
- the physical properties of the sorbent were determined, and are shown below compared to a sulphided copper sorbent prepared using basic copper carbonate, cement and clay binders, and an alumina trihydrate (ATH) support material, according to the method described in WO2009/101429 .
- the tapped bulk density was measured by pouring approximately 500mls of sorbent granules into a 500ml plastic measuring cylinder and tapping it until a constant volume was achieved.
- the TBD was calculated by dividing the mass of sorbent by the tapped volume.
- the drum tumbling loss (DrTL) was measured by rotating 100g of sorbent through 1800 total revolutions at 60 rpm for 30 minutes according to the ASTM method D4058-96. The DrTL is reported as a percentage of the original mass.
- the mean crush strength (MCS) was determined by crushing 25 granules of each sorbent using an Engineering Systems C53 machine to calculate mean crush strength based on a normal distribution.
- a calcined, rehydratable alumina provided a much stronger product when compared to the prior art material produced using mixed binders and aluminium trihydrate.
- the rate at which strength develops also occurs much more rapidly in the calcined, rehydratable alumina product when compared to the mixed binder product with strength achieved over 5 times higher following 1 hour of ageing.
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Description
- This invention relates to a method for preparing a sorbent based on a mixture consisting of a particulate copper sulphide and a particulate calcined, rehydratable alumina.
- Copper sulphide containing sorbents are useful in removing heavy metals from fluid streams. Heavy metals such as mercury are found in small quantities in fluid streams such as hydrocarbon or other gas and liquid streams. Arsenic and antimony may also be found in small quantities in hydrocarbon streams. Mercury, in addition to its toxicity, can cause failure of aluminium heat exchangers and other processing equipment. Therefore there is a need to efficiently remove these metals from fluid streams, preferably as early as possible in the process flowsheet.
- Copper sulphide is conventionally formed in the sorbents either in situ by reaction of a sorbent precursor containing a sulphidable copper compound with hydrogen sulphide (H2S) present in the fluid stream, or by pre-sulphiding the sorbent precursor again with hydrogen sulphide. This reaction is depicted for copper oxide as follows:
CuO + H2S → CuS + H2O
- Similarly, where copper hydroxycarbonate materials are used, both CO2 and H2O are evolved.
-
WO2009/101429 discloses a method for making an absorbent comprising the steps of: (i) forming a composition comprising a particulate copper compound capable of forming copper sulphide, a particulate support material, and one or more binders, (ii) shaping the composition to form an absorbent precursor, (iii) drying the absorbent precursor material, and (iv) sulphiding the precursor to form the absorbent. The sulphiding agent used to sulphide the absorbent precursor may be one or more sulphur compounds such as hydrogen sulphide, carbonyl sulphide, mercaptans and polysulphides, or mixtures of these. Hydrogen sulphide is preferred. -
US2013202503 discloses a process for removing mercury from a fluid stream comprising contacting the fluid stream with a sorbent comprising cupric sulfide. The cupric sulfide is formed from direct sulfidation of copper carbonate, without thermal decomposition of the copper carbonate to an oxide, at a temperature less than about 150° C. -
WO2011081836 discloses a process for the removal of mercury from a mixture of saturated and unsaturated hydrocarbons such as from cracked gas. The gas first is contained in a regenerable adsorbent bed that removes water and mercury and then the regenerant stream for the adsorbent bed is passed through a non-regenerable bed comprising copper sulfide to trap the mercury. -
US2014155260 discloses a process for removing mercury from a gas or liquid phase, wherein the gas or liquid phase containing mercury is placed in contact with a composition comprising a precipitated metal sulfide. The precipitated metal sulfide may be made by the process of combining a metal source, sulfide source, and modifier to form the precipitated metal sulfide. -
US2007122327 discloses sorbents for removal of mercury and other pollutants from gas streams and methods for their manufacture and use. The methods include mixing sorbent substrate particles with a sulfide salt and a metal salt to form a metal sulfide on the outer surface of the sorbent particles. - It was believed that the conversion of the copper compounds was necessary in order to provide a sorbent with suitable physical properties and effective capacity for heavy metals. However, the sulphiding method using these sulphiding agents if not carefully controlled can lead to inhomogeneous product and impaired physical properties. Moreover hydrogen sulphide is a toxic gas and control measures are necessary for sulphiding at large scale. Therefore there is a need to seek alternative methods that are inherently safer, simpler and offer improved product homogeneity.
- There is also a need to improve the product physical properties, notably the crush strength, which presently relies on the use of one or more binders.
- We have found that replacing the particulate support material and binder combination with a particulate calcined, rehydratable alumina improves the sorbent properties.
- Accordingly the invention provides a method for preparing a sorbent comprising the steps of:
- (i) forming a mixture consisting of a particulate copper sulphide and a particulate calcined, rehydratable alumina,
- (ii) shaping the mixture, and
- (iii) drying the shaped mixture to form a dried sorbent.
- The invention further provides a method for removing heavy metals such as mercury, arsenic selenium, cadmium and antimony, from heavy metal-containing fluid stream by preparing a sorbent according with the above method and contacting the fluid stream with the sorbent.
- By "sorbent" we include absorbent and adsorbent.
- By "calcined, rehydratable alumina" we mean a calcined amorphous or poorly crystalline transition alumina comprising one or more of rho-, chi- and pseudo gamma-aluminas. Such aluminas are capable of rehydration and can retain substantial amounts of water in a reactive form. Calcined, rehydratable aluminas are commercially available, for example as "CP alumina powders" available from BASF AG. They may be prepared, for example, by milling gibbsite (Al(OH)3), to a 1-20 micron particle size followed by flash calcination for a short contact time as described in
U.S. patent No. 2,915,365 . In addition to gibbsite, amorphous aluminum hydroxide and other naturally found mineral crystalline hydroxides such as Bayerite and Nordstrandite or monoxide hydroxides, such as Boehmite (AIOOH) and Diaspore may be also used as a source of the calcined, rehydratable alumina. - The particulate copper sulphide used to prepare the sorbent may be sourced commercially or may be prepared by a number of methods. Suitable methods include roasting of copper or a copper compound with elemental sulphur, solvothermal processes, hydrothermal processes (e.g. microwave irradiation), electrodeposition techniques, precipitation of copper sulphide from solution, sulphiding of copper compounds using hydrogen sulphide, electron irradiation or by a mechanochemical process in which powdered copper metal is mixed with elemental sulphur under conditions that cause the elemental copper and elemental sulphur to react to form one or more copper sulphides. Such methods are described in the Materials Research Bulletin, vol 30, no 12, p1495-1504, 1995 .
- Copper sulphides that may be used include Copper (II) sulphide, CuS, (covellite) and/or substoichiometric copper sulphides, e.g. of formula Cu2-xS where x is 0-1, such as Cu9S5 (digenite). One or more copper sulphides may be used. Copper sulphides high in CuS are preferred, and the overall S:Cu atomic ratio of the particulate copper sulphide is preferably ≥ 0.8, more preferably ≥ 0.9, most preferably ≥ 0.95. Desirably, essentially all of the sulphided copper in the sorbent is in the form of copper (II) sulphide, CuS. The particulate copper sulphide may be in the form of a powder, preferably a powder with an average particle size, i.e. Dso, in the range 5-100µm.
- The dried sorbent may comprise 5-75% by weight, preferably 10-75% by weight, more preferably 15-55% by weight, especially 15-50% by weight, of copper sulphide (expressed as CuS).
- The particulate calcined, rehydratable alumina is preferably an amorphous or poorly crystalline transition alumina comprising one or more of rho-alumina, chi-alumina and pseudo-gamma alumina. Preferably the particulate calcined, rehydratable alumina consists of one or more of rho-alumina, chi-alumina and pseudo-gamma alumina, especially rho-alumina. The particulate calcined, rehydratable alumina is desirably in the form of a powder, more preferably a powder with a D50 particle size in the range 1-100µm, preferably 1-20µm, especially 1-10µm. The BET Surface area of the calcined, rehydratable alumina as determined by nitrogen adsorption may be in the range 200-400m2/g, preferably 250-300m2/g.
- The dried sorbent may comprise 25-95% by weight, preferably 25-90% by weight, of the particulate calcined, rehydratable alumina.
- We have found that no other additives are necessary and therefore that the first step in the method for preparing the sorbent comprises forming a mixture consisting of the particulate copper sulphide and the particulate calcined, rehydratable alumina.
- The sorbent may be considered to be "binderless".
- The sorbent is made from a mixture that consists of copper sulphide and the particulate calcined, rehydratable alumina.
- The mixture consisting of copper sulphide and particulate calcined, rehydratable alumina is shaped and dried to form the sorbent. Shaping may be by pelleting, extruding or granulating. Hence, sorbent pellets may be formed by moulding a powder composition, generally containing a material such as graphite or magnesium stearate as a moulding aid, in suitably sized moulds, e.g. as in conventional tableting operation. Alternatively, sorbent extrudates may be formed by forcing a suitable composition and often a little water and/or a moulding aid as indicated above, through a die followed by cutting the material emerging from the die into short lengths. For example extrudates may be made using a pellet mill of the type used for pelleting animal feedstuffs, wherein the mixture to be pelleted is charged to a rotating perforate cylinder through the perforations of which the mixture is forced by a bar or roller within the cylinder: the resulting extruded mixture is cut from the surface of the rotating cylinder by a doctor knife positioned to give extruded pellets of the desired length. Alternatively, sorbent granules, in the form of agglomerates, may be formed by mixing a powder composition with a little liquid, such as water, insufficient to form a slurry, and then causing the composition to agglomerate into roughly spherical granules in a granulator. The amount of liquid added will vary depending upon the porosity and wettability of the components, but may be 0.1 to 0.5 ml/g of support mixture. Aqueous or non-aqueous liquids may be used, but water is preferred. Minimizing the amount of liquid used advantageously reduces the drying time of the sorbent and may reduce the formation of undesirable copper sulphates. Similarly, granulating the mixture under a non-oxidising atmosphere, such as oxygen-free nitrogen, reduces the potential formation of sulphates. Suitable granulator equipment is available commercially. The liquid may be conveniently added by spraying.
- The pellets, extrudates or granules preferably have a length and width in the range 1 to 25 mm, with an aspect ratio (longest dimension divided by shortest dimension) ≤ 4.
- The different shaping methods have an effect on the surface area, porosity and pore structure within the shaped articles and in turn this often has a significant effect on the sorption characteristics and on the bulk density. Thus beds of sorbents in the form of moulded pellets may exhibit a relatively broad absorption front, whereas beds of granulated agglomerates can have a much sharper absorption front: this enables a closer approach to be made to the theoretical absorption capacity. On the other hand, agglomerates generally have lower bulk densities than tableted compositions. Furthermore, in view of the presence of copper sulphide, methods involving small amounts of water are preferred to avoid possible sulphate formation, which is undesirable. Accordingly, it is preferred to make the shaped units in the form of agglomerates and thus a preferred shaping method involves granulating the mixture of copper sulphide and calcined, rehydratable alumina in a granulator. Granules with a diameter in the range 1-15 mm are preferred. The amount of water used in granulating the mixtures has been found to have an influence on the strength of the resulting granules. The amount of water used in the granulation may be in the range 0.25ml/g of powder to 0.6ml/g of the mixture of copper sulphide and calcined, rehydratable alumina. This is higher than the prior art granulated products that typically require <0.2ml/g of mixture and arises from the unusual properties of the calcined, rehydratable alumina.
- The shaped absorbent may be aged to enhance its strength before drying. Ageing of the calcined, rehydratable alumina-containing sorbents is suitably performed at 20-90°C, preferably 40-90°C. An advantage of using just the calcined, rehydratable alumina in the sorbent is that the ageing step may be considerably reduced or eliminated compared to prior art materials. Thus ageing may be performed on calcined, rehydratable alumina containing granules for 0.5 - 8 hours, preferably 0.5-6 hours, more preferably 0.5-2 hours before drying. Ageing under a non-oxidising atmosphere such as dry nitrogen reduces the potential for sulphate formation.
- The shaped sorbent is dried. Conventional drying equipment may be used. Drying temperatures up to 120°C may be used. Drying times may be in the range 0.25-16 hours. Drying under a non-oxidising atmosphere such as dry nitrogen reduces the potential for sulphate formation.
- The sorbent may be used to treat both liquid and gaseous fluid streams containing heavy metals, in particular fluids containing mercury and/or arsenic. In one embodiment, the fluid stream is a hydrocarbon stream. The hydrocarbon stream may be a refinery hydrocarbon stream such as naphtha (e.g. containing hydrocarbons having 5 or more carbon atoms and a final atmospheric pressure boiling point of up to 204°C), middle distillate or atmospheric gas oil (e.g. having an atmospheric pressure boiling point range of 177°C to 343°C), vacuum gas oil (e.g. atmospheric pressure boiling point range 343°C to 566°C), or residuum (atmospheric pressure boiling point above 566°C), or a hydrocarbon stream produced from such a feedstock by e.g. catalytic reforming. Refinery hydrocarbon steams also include carrier streams such as "cycle oil" as used in FCC processes and hydrocarbons used in solvent extraction. The hydrocarbon stream may also be a crude oil stream, particularly when the crude oil is relatively light, or a synthetic crude stream as produced from tar oil or coal extraction for example. Gaseous hydrocarbons may be treated using the process of the invention, e.g. natural gas or refined paraffins or olefins, for example. Off-shore crude oil and off-shore natural gas streams in particular may be treated with the sorbent. Contaminated fuels such as petrol or diesel may also be treated. Alternatively, the hydrocarbon may be a condensate such as natural gas liquid (NGL) or liquefied petroleum gas (LPG), or gases such as a coal bed methane, landfill gas or biogas. Gaseous hydrocarbons, such as natural gas and associated gas are preferred.
- Non-hydrocarbon fluid streams which may be treated include carbon dioxide, which may be used in enhanced oil recovery processes or in carbon capture and storage, solvents for decaffeination of coffee, flavour and fragrance extraction, solvent extraction of coal etc. Fluids, such as alcohols (including glycols) and ethers used in wash processes or drying processes (e.g. triethylene glycol, monoethylene glycol, Rectisol™, Purisol™ and methanol), may be treated by the inventive process. Mercury may also be removed from amine streams used in acid gas removal units. Natural oils and fats such as vegetable and fish oils may be treated, optionally after further processing such as hydrogenation or transesterification e.g. to form biodiesel.
- Other fluid streams that may be treated include the regeneration gases from dehydration units, such as molecular sieve off-gases, or gases from the regeneration of glycol driers.
The sorbent is of utility where the fluid stream contains water, preferably in low levels in the range 0.02 to 1% vol. Higher levels up to 5% vol may be tolerated for short periods. The sorbents may be regenerated simply after prolonged exposure to water simply by purging with a dry gas, preferably a dry inert gas such as nitrogen. - Preferably the sorption of heavy metal is conducted at a temperature below 150°C, preferably at or below 120°C in that at such temperatures the overall capacity for heavy metal absorption is increased. Temperatures as low as 4°C may be used. A preferred temperature range is 10 to 60°C. The gas hourly space velocity through the sorbent may be in the range normally employed.
- Furthermore, the sorbent may be used to treat both liquid and gaseous fluid streams containing one or more reductants such as hydrogen and/or carbon monoxide, notably hydrogen. In one embodiment, the fluid stream is a liquid hydrocarbon stream containing dissolved hydrogen and/or carbon monoxide. In another embodiment, the fluid stream is a gaseous stream containing hydrogen and/or carbon monoxide, i.e. a reducing gas stream. Gas streams that may benefit from this process include synthesis gas streams from conventional steam reforming processes and/or partial oxidation processes, and synthesis gas streams from a coal gasifier, e.g. as part of a IGCC process, after gas washing and heat recovery (cooling) steps, and before the sour shift stage. Other streams that may benefit from the present invention include refinery vent streams, refinery cracker streams, blast furnace gases, reducing gases, particularly hydrogen-rich gas streams, ethylene-rich streams and liquid or gaseous hydrocarbon streams, e.g. naphtha, fed or recovered from hydrotreating processes, such as hydrodesulphurisation or hydrodenitrification.
- In use, the sorbent may be placed in a sorption vessel and the fluid stream containing heavy metal is passed through it. Desirably, the sorbent is placed in the vessel as one or more fixed beds according to known methods. More than one bed may be employed and the beds may be the same or different in composition.
- The invention is further described by reference to the following Examples.
- A mixture of a copper sulphide powder and a calcined, rehydratable alumina powder was prepared as follows:
Component Source % wt Copper sulphide (99%), Eurolub 33 Calcined, rehydratable alumina CP-5, BASF 67 - The properties of the calcined, rehydratable alumina powder were as follows:
Chemical composition (wt %) Residual Moisture (dried a 250°C for 30 minutes) 2 Total loss on ignition (250-1100°C) 7 SiO2 <0.02 Fe2O3 <0.01 Na2O <0.4 Physical Properties BET Surface area 270 m2/g Packed bulk density 38 Ib/ft3 Particle size distribution (average size) 5µm Particle size distribution (90 wt% <) 12µm XRD Phase Amorphous - The powders were pre-mixed to ensure a homogenous mixture. Granules were then formed by nodulizing the mixture in a rotating pan while water (about 0.33ml/g mixture) was sprayed onto the mixture as a fine mist. The water was found to be about 25 wt% of the mass of the shaped agglomerates before drying. This is significantly higher than the water content of the prior granulated sorbents which typically only comprise about 15 wt% water. Following granulation, the material was aged at 45°C. Following ageing, the material was dried in a fluid bed dryer at 105°C, to produce the sorbent.
- The physical properties of the sorbent were determined, and are shown below compared to a sulphided copper sorbent prepared using basic copper carbonate, cement and clay binders, and an alumina trihydrate (ATH) support material, according to the method described in
WO2009/101429 . - The tapped bulk density (TBD) was measured by pouring approximately 500mls of sorbent granules into a 500ml plastic measuring cylinder and tapping it until a constant volume was achieved. The TBD was calculated by dividing the mass of sorbent by the tapped volume. The drum tumbling loss (DrTL) was measured by rotating 100g of sorbent through 1800 total revolutions at 60 rpm for 30 minutes according to the ASTM method D4058-96. The DrTL is reported as a percentage of the original mass.
- The mean crush strength (MCS) was determined by crushing 25 granules of each sorbent using an Engineering Systems C53 machine to calculate mean crush strength based on a normal distribution.
Example Ageing time (h) TBD (g cm-3) DrTL (%) MCS (kgF) 1(a) 1 1.04 0.00 7.61 1(b) 6 1.04 n/a 8.51 1(c) 6 1.02 0.00 8.89 1(d) 24 1.03 n/a 9.91 1(e) 24 1.04 0.00 9.55 Comparative 12 0.99 2.20 1.48 - The use of a calcined, rehydratable alumina provided a much stronger product when compared to the prior art material produced using mixed binders and aluminium trihydrate. The rate at which strength develops also occurs much more rapidly in the calcined, rehydratable alumina product when compared to the mixed binder product with strength achieved over 5 times higher following 1 hour of ageing.
Claims (14)
- A method for preparing a sorbent comprising the steps of:(i) forming a mixture consisting of a particulate copper sulphide and a particulate calcined, rehydratable alumina,(ii) shaping the mixture, and(iii) drying the shaped mixture to form a dried sorbent.
- A method according to claim 1 wherein the calcined rehydratable alumina comprises a calcined amorphous alumina or a transition alumina selected from one or more of rho-alumina, chi-alumina and pseudo gamma-alumina.
- A method according to claim 1 or claim 2 wherein the particulate copper sulphide material is manufactured by either roasting of copper or a copper compound with elemental sulphur, precipitation of copper sulphide from solution, sulphiding of copper compounds using hydrogen sulphide, or a mechanochemical process in which powdered copper metal is mixed with elemental sulphur under conditions that cause the elemental copper and elemental sulphur to react to form one or more copper sulphides.
- A method according to any one of claims 1 to 3 wherein the copper sulphide comprises one or more copper sulphides selected from copper (II) sulphide, CuS, and/or substoichiometric copper sulphides of formula Cu2-xS where x is 0-1,
- A method according to any one of claims 1 to 4 wherein the particulate copper sulphide has an overall S:Cu atomic ratio of ≥ 0.8, preferably ≥ 0.9, more preferably ≥ 0.95.
- A method according to any one of claims 1 to 5 wherein the particulate copper sulphide material is in the form of a powder with an average particle size, [D50], in the range 5-100µm.
- A method according to any one of claims 1 to 6 wherein the copper content of the dried sorbent is in the range 5-75% by weight (expressed as CuS), preferably 10-75% by weight, more preferably 15-55% by weight and especially15-50% by weight.
- A method according to any one of claims 1 to 7 wherein the particulate calcined rehydratable alumina is a powder with a D50 particle size in the range 1-100µm, preferably 1-20µm, especially 1-10µm.
- A method according to any one of claims 1 to 8 wherein the BET Surface area of the calcined rehydratable alumina as determined by nitrogen adsorption is in the range 200-400m2/g, preferably 250-300m2/g.
- A method according to any one of claims 1 to 9 wherein the shaping step comprises granulating the mixture in a granulator to produce the sorbent in the form of granules.
- A method according to claim 10 wherein the granulation is performed under a non-oxidising atmosphere.
- A method according to claim 10 or claim 11 wherein the granules are aged for 0.5 - 8 hours, preferably 0.5 - 6 hours, more preferably 0.5 - 2 hours before drying.
- A method according to any one of claims 1 to 12 wherein the sorbent is dried at a temperature up to 120°C under a non-oxidising atmosphere.
- A process for removing one or more heavy metals from a heavy metal-containing fluid stream by preparing a sorbent according to the method of any one of claims 1 to 13 and contacting the fluid stream with the sorbent.
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CN107787249B (en) | 2021-06-11 |
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